US2530367A - Disproportionation of alkoxysilanes - Google Patents
Disproportionation of alkoxysilanes Download PDFInfo
- Publication number
- US2530367A US2530367A US790230A US79023047A US2530367A US 2530367 A US2530367 A US 2530367A US 790230 A US790230 A US 790230A US 79023047 A US79023047 A US 79023047A US 2530367 A US2530367 A US 2530367A
- Authority
- US
- United States
- Prior art keywords
- temperature
- group
- alkoxysilane
- silane
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000007323 disproportionation reaction Methods 0.000 title description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical group [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 alkali metal alkoxide Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/04—Hydrides of silicon
- C01B33/043—Monosilane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
Definitions
- the invention is a process for disproportionating alkoxysilanes. It affords a means of effecting, in an assemblage of silicon-containing molecules each comprising at least one hydrogen atom and at least one alkoxy group, a redistribution in such fashion that silicon-containing molecules devoid of alkoxy groups are formed concomitantly with silicon-containing molecules in which no Si-H bond is present.
- triethoxysilane SiH(OC2H5) 3 a readily available compound, can be caused to undergo the transformation depicted by the equation Valuable products are thereby formed-in this example silane and tetraethylorthosilicate.
- the disproportionation is carried out by treating the allroxysilane with a suitable catalyst at an appropriate temperature.
- a suitable catalyst we prefer a compound of the type represented by the formula MOE, where M is a metal of group IA of the periodic table, and R is hydrogen or an alkyl group.
- MOE metal of group IA of the periodic table
- R is hydrogen or an alkyl group.
- the hydroxides and ethoxides of sodium and potassium are preferred.
- the quantity of catalyst used is not critical, and since the preferred catalysts are inexpensive substances, 0.5 or more has been used in most of our tests.
- the temperature employed may range from room temperature or below to moderate heating, for example to 60 C. Raising the temperature accelerates the reaction but may reduce the chiciency, as by causing hydrogen to appear in considerable proportions in the gaseous product. Even at room temperatures the velocity of the reaction is such as to be adequate in many cases.
- silane when 0.65% of NaOCzHa was added to 7.5 g. of SiI-I(OC2H5)3 at 26 0., silane was evolved at the rate of 3.3 cc. per minute; at 40 C. the rate increased to 4.4 cc./min., and at 60 C. to 8/1 cc./min. Increasing the proportion of ethoxide catalyst to 2.1% gave 20.7 cc./min. of silane at 26 C.
- the hydroxides show activity of the same order as the ethoxides. If a very rapid evolution of gas is desired, as in some prospective applications of the invention, either the proportion of catalyst or the temperature or both are increased.
- ThllSfWith 1 of NaOH at 60 C. silane (containing some 30% of Hz) was evolved at the rate of more than 50 cc./min. from a 7.5 g. sample of SiH(OC2I-I5)3.
- Process of disproportionating an alkoxysilane containing at least one hydrogen atom at tached to silicon which comprises treating said alkoxysilane, at a temperature not substantially above about C., with a compound in solid form having the type formula MOR, Where M is a metal of group IA of the periodic table, and R is a member of the group consisting of hydrogen and alkyl radicals, and recovering silane from the reaction product.
- Process of disproportionating an alkoxysilane containing at least one hydrogen atom attached to silicon which comprises treating said alkoxysilane, at a temperature not substantially above about 60 C., with a solid alkali metal alkoxide, and recovering silane from the reaction product.
- Process of disproportionating an alkoxysilane containing at least one hydrogen atom attached to silicon which comprises treating said alkoxysilane, at a temperature not substantially above about 60 C., with a solid alkali metal hydroxide, and recovering silane from the reaction product.
- Process of disproportionating a trialkoxysilane which comprises treating it, at a temperature not substantially above about 60 C., with a solid alkali metal alkoxide, and recovering silane from the reaction product.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Description
Patented Nov. 21, 1950 DISPROPORTIONATION OF ALKOXYSILANES Charles R. Hance, Durham, N. 0., and George H. Wagner, Kenmore, N. Y., assignors to The Linde Air Products Company, a corporation of Ohio No Drawing. Application December 6, 1947, Serial No. 790,230
Claims.
The invention is a process for disproportionating alkoxysilanes. It affords a means of effecting, in an assemblage of silicon-containing molecules each comprising at least one hydrogen atom and at least one alkoxy group, a redistribution in such fashion that silicon-containing molecules devoid of alkoxy groups are formed concomitantly with silicon-containing molecules in which no Si-H bond is present. Thus, triethoxysilane SiH(OC2H5) 3 a readily available compound, can be caused to undergo the transformation depicted by the equation Valuable products are thereby formed-in this example silane and tetraethylorthosilicate.
The disproportionation is carried out by treating the allroxysilane with a suitable catalyst at an appropriate temperature. For the catalyst we prefer a compound of the type represented by the formula MOE, where M is a metal of group IA of the periodic table, and R is hydrogen or an alkyl group. The hydroxides and ethoxides of sodium and potassium are preferred. The quantity of catalyst used is not critical, and since the preferred catalysts are inexpensive substances, 0.5 or more has been used in most of our tests.
The temperature employed may range from room temperature or below to moderate heating, for example to 60 C. Raising the temperature accelerates the reaction but may reduce the chiciency, as by causing hydrogen to appear in considerable proportions in the gaseous product. Even at room temperatures the velocity of the reaction is such as to be adequate in many cases. Thus, when 0.65% of NaOCzHa was added to 7.5 g. of SiI-I(OC2H5)3 at 26 0., silane Was evolved at the rate of 3.3 cc. per minute; at 40 C. the rate increased to 4.4 cc./min., and at 60 C. to 8/1 cc./min. Increasing the proportion of ethoxide catalyst to 2.1% gave 20.7 cc./min. of silane at 26 C. The hydroxides show activity of the same order as the ethoxides. If a very rapid evolution of gas is desired, as in some prospective applications of the invention, either the proportion of catalyst or the temperature or both are increased. ThllSfWith 1 of NaOH at 60 C. silane (containing some 30% of Hz) was evolved at the rate of more than 50 cc./min. from a 7.5 g. sample of SiH(OC2I-I5)3.
What is claimed is:
1. Process of disproportionating an alkoxysilane containing at least one hydrogen atom at tached to silicon, which comprises treating said alkoxysilane, at a temperature not substantially above about C., with a compound in solid form having the type formula MOR, Where M is a metal of group IA of the periodic table, and R is a member of the group consisting of hydrogen and alkyl radicals, and recovering silane from the reaction product.
2. Process of disproportionating an alkoxysilane containing at least one hydrogen atom attached to silicon, which comprises treating said alkoxysilane, at a temperature not substantially above about 60 C., with a solid alkali metal alkoxide, and recovering silane from the reaction product.
3. Process of disproportionating an alkoxysilane containing at least one hydrogen atom attached to silicon, which comprises treating said alkoxysilane, at a temperature not substantially above about 60 C., with a solid alkali metal hydroxide, and recovering silane from the reaction product.
4. Process of disproportionating a trialkoxysilane which comprises treating it, at a temperature not substantially above about 60 C., with a solid alkali metal alkoxide, and recovering silane from the reaction product.
5. Process of disproportionating triethoXysilane which comprises treating it, at a temperature not substantially above about 60 C., with a compound in solid form having the type formula MOR, Where M is a metal of group IA of the periodic table, and R is a member of the group consisting of hydrogen and alkyl radicals, and recovering silane from the reaction product.
CHARLES R. HANCE. GEORGE H. WAGNER.
REFERENCES CITED The following references are of record in the file of this patent:
Friedel: Annalen der Chemie, vol. 143. (1867) pages 124-127.
Taurke: Berichte, vol. 38 (1905) pages 1661, 1662.
Post: The Chemistry of Aliphatic Ortho Esters, page 146, 147. Published by Reinhold. N. Y., 1943.
Claims (1)
1. PROCESS OF DISPORPORTIONATING AN ALKOXYSILANE CONTAINING AT LEAST ONE HYDROGEN ATOM ATTACHED TO SILICON, WHICH COMPRISES TREATING SAID ALKOXYSILANE, AT A TEMPERATURE NOT SUBSTANTAILLY ABOVE ABOUT 60*C., WITH A COMPOUND IN SOLID FORM HAVING THE TYPE FORMULA MOR, WHERE M IS A METAL OF GROUP IA OF THE PERIODIC TABLE, AND R IS A MEMBER OF THE GROUP CONSISTING OF HYDROGEN AND ALKYL RADICALS, AND RECOVERING SILANE FROM THE REACTION PRODUCT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US790230A US2530367A (en) | 1947-12-06 | 1947-12-06 | Disproportionation of alkoxysilanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US790230A US2530367A (en) | 1947-12-06 | 1947-12-06 | Disproportionation of alkoxysilanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2530367A true US2530367A (en) | 1950-11-21 |
Family
ID=25150035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US790230A Expired - Lifetime US2530367A (en) | 1947-12-06 | 1947-12-06 | Disproportionation of alkoxysilanes |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2530367A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2723985A (en) * | 1952-10-17 | 1955-11-15 | Union Carbide & Carbon Corp | Disproportionation of allyl- and butenylalkoxysilanes |
| US2723983A (en) * | 1952-10-16 | 1955-11-15 | Union Carbide & Carbon Corp | Disproportionation of hydrocarbon alkoxysilanes |
| US2723984A (en) * | 1952-10-17 | 1955-11-15 | Union Carbide & Carbon Corp | Disproportionation of arylalkoxysilanes |
| US2735861A (en) * | 1956-02-21 | Disproportionation of alkoxy silane | ||
| US2745860A (en) * | 1952-10-16 | 1956-05-15 | Union Carbide & Carbon Corp | Disproportionation of alkoxydisilyl hydrocarbons |
| US3463660A (en) * | 1965-05-11 | 1969-08-26 | Ici Ltd | Process for obtaining an anti-stick surface with an organosilicon and an organopolysiloxane and a cooking utensil so treated |
| DE2247873A1 (en) * | 1971-10-01 | 1973-04-05 | Tokyo Shibaura Electric Co | PROCESS FOR THE PRODUCTION OF SILANES |
| EP0337322A3 (en) * | 1988-04-13 | 1991-03-27 | Mitsubishi Kasei Corporation | Process for producing monosilane |
| US5126472A (en) * | 1991-11-12 | 1992-06-30 | Dow Corning Corporation | Thermal disproportionation of organooxysilanes |
| US5126471A (en) * | 1991-11-14 | 1992-06-30 | Dow Corning Corporation | Thermal disproportionation of cycloalkylsilanes |
| RU2279403C1 (en) * | 2004-12-27 | 2006-07-10 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП ГНИИХТЭОС) | High-purity monosilane production process |
| WO2014054889A1 (en) | 2012-10-02 | 2014-04-10 | 오씨아이 주식회사 | Method for preparing monosilane using trialkoxysilane |
-
1947
- 1947-12-06 US US790230A patent/US2530367A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2735861A (en) * | 1956-02-21 | Disproportionation of alkoxy silane | ||
| US2723983A (en) * | 1952-10-16 | 1955-11-15 | Union Carbide & Carbon Corp | Disproportionation of hydrocarbon alkoxysilanes |
| US2745860A (en) * | 1952-10-16 | 1956-05-15 | Union Carbide & Carbon Corp | Disproportionation of alkoxydisilyl hydrocarbons |
| US2723985A (en) * | 1952-10-17 | 1955-11-15 | Union Carbide & Carbon Corp | Disproportionation of allyl- and butenylalkoxysilanes |
| US2723984A (en) * | 1952-10-17 | 1955-11-15 | Union Carbide & Carbon Corp | Disproportionation of arylalkoxysilanes |
| US3463660A (en) * | 1965-05-11 | 1969-08-26 | Ici Ltd | Process for obtaining an anti-stick surface with an organosilicon and an organopolysiloxane and a cooking utensil so treated |
| DE2247873A1 (en) * | 1971-10-01 | 1973-04-05 | Tokyo Shibaura Electric Co | PROCESS FOR THE PRODUCTION OF SILANES |
| EP0337322A3 (en) * | 1988-04-13 | 1991-03-27 | Mitsubishi Kasei Corporation | Process for producing monosilane |
| US5126472A (en) * | 1991-11-12 | 1992-06-30 | Dow Corning Corporation | Thermal disproportionation of organooxysilanes |
| EP0542243A1 (en) * | 1991-11-12 | 1993-05-19 | Dow Corning Corporation | Thermal disproportionation of organooxysilanes |
| US5126471A (en) * | 1991-11-14 | 1992-06-30 | Dow Corning Corporation | Thermal disproportionation of cycloalkylsilanes |
| RU2279403C1 (en) * | 2004-12-27 | 2006-07-10 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП ГНИИХТЭОС) | High-purity monosilane production process |
| WO2014054889A1 (en) | 2012-10-02 | 2014-04-10 | 오씨아이 주식회사 | Method for preparing monosilane using trialkoxysilane |
| US9278864B2 (en) | 2012-10-02 | 2016-03-08 | Oci Company Ltd. | Method for preparing monosilane using trialkoxysilane |
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